CN112919522A - Cerium oxide material and preparation method and application thereof - Google Patents
Cerium oxide material and preparation method and application thereof Download PDFInfo
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- CN112919522A CN112919522A CN201911243695.5A CN201911243695A CN112919522A CN 112919522 A CN112919522 A CN 112919522A CN 201911243695 A CN201911243695 A CN 201911243695A CN 112919522 A CN112919522 A CN 112919522A
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- 229910000420 cerium oxide Inorganic materials 0.000 title claims abstract description 87
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 title claims abstract description 87
- 239000000463 material Substances 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 37
- 239000007788 liquid Substances 0.000 claims abstract description 24
- 239000011258 core-shell material Substances 0.000 claims abstract description 20
- 239000006185 dispersion Substances 0.000 claims abstract description 20
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 18
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 12
- 229920000642 polymer Polymers 0.000 claims abstract description 12
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 7
- 230000003746 surface roughness Effects 0.000 claims abstract description 7
- 238000003756 stirring Methods 0.000 claims description 37
- 239000011259 mixed solution Substances 0.000 claims description 34
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 24
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims description 24
- 239000003570 air Substances 0.000 claims description 22
- 239000012298 atmosphere Substances 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- 239000000243 solution Substances 0.000 claims description 16
- 238000010992 reflux Methods 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 12
- 235000010299 hexamethylene tetramine Nutrition 0.000 claims description 12
- 239000004312 hexamethylene tetramine Substances 0.000 claims description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 11
- 229910052799 carbon Inorganic materials 0.000 claims description 11
- 239000003054 catalyst Substances 0.000 claims description 9
- 238000001354 calcination Methods 0.000 claims description 7
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 229920001568 phenolic resin Polymers 0.000 claims description 6
- 239000005011 phenolic resin Substances 0.000 claims description 6
- 239000004793 Polystyrene Substances 0.000 claims description 5
- 239000000919 ceramic Substances 0.000 claims description 5
- 239000011521 glass Substances 0.000 claims description 5
- 238000005498 polishing Methods 0.000 claims description 5
- 229920002223 polystyrene Polymers 0.000 claims description 5
- 230000001376 precipitating effect Effects 0.000 claims description 5
- 238000000746 purification Methods 0.000 claims description 5
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 4
- 150000000703 Cerium Chemical class 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- 150000001412 amines Chemical class 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 239000002270 dispersing agent Substances 0.000 claims description 4
- 239000003822 epoxy resin Substances 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 229920000647 polyepoxide Polymers 0.000 claims description 4
- -1 polyethylene Polymers 0.000 claims description 4
- 239000002243 precursor Substances 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 239000001307 helium Substances 0.000 claims description 3
- 229910052734 helium Inorganic materials 0.000 claims description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 2
- 239000004698 Polyethylene Substances 0.000 claims description 2
- 239000004743 Polypropylene Substances 0.000 claims description 2
- 239000011358 absorbing material Substances 0.000 claims description 2
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 claims description 2
- VGBWDOLBWVJTRZ-UHFFFAOYSA-K cerium(3+);triacetate Chemical compound [Ce+3].CC([O-])=O.CC([O-])=O.CC([O-])=O VGBWDOLBWVJTRZ-UHFFFAOYSA-K 0.000 claims description 2
- OZECDDHOAMNMQI-UHFFFAOYSA-H cerium(3+);trisulfate Chemical compound [Ce+3].[Ce+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O OZECDDHOAMNMQI-UHFFFAOYSA-H 0.000 claims description 2
- MOOUSOJAOQPDEH-UHFFFAOYSA-K cerium(iii) bromide Chemical compound [Br-].[Br-].[Br-].[Ce+3] MOOUSOJAOQPDEH-UHFFFAOYSA-K 0.000 claims description 2
- 229920000573 polyethylene Polymers 0.000 claims description 2
- 229920001155 polypropylene Polymers 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 239000007789 gas Substances 0.000 claims 1
- 238000001035 drying Methods 0.000 abstract description 13
- 238000005406 washing Methods 0.000 abstract description 13
- 239000002086 nanomaterial Substances 0.000 abstract description 5
- 239000012716 precipitator Substances 0.000 abstract description 5
- 239000003960 organic solvent Substances 0.000 abstract description 2
- 238000000926 separation method Methods 0.000 description 11
- 239000008367 deionised water Substances 0.000 description 10
- 229910021641 deionized water Inorganic materials 0.000 description 10
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 230000001788 irregular Effects 0.000 description 3
- 238000001000 micrograph Methods 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 2
- 239000011324 bead Substances 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- LHLMOSXCXGLMMN-CLTUNHJMSA-M [(1s,5r)-8-methyl-8-propan-2-yl-8-azoniabicyclo[3.2.1]octan-3-yl] 3-hydroxy-2-phenylpropanoate;bromide Chemical compound [Br-].C([C@H]1CC[C@@H](C2)[N+]1(C)C(C)C)C2OC(=O)C(CO)C1=CC=CC=C1 LHLMOSXCXGLMMN-CLTUNHJMSA-M 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- DRVWBEJJZZTIGJ-UHFFFAOYSA-N cerium(3+);oxygen(2-) Chemical group [O-2].[O-2].[O-2].[Ce+3].[Ce+3] DRVWBEJJZZTIGJ-UHFFFAOYSA-N 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000002073 nanorod Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
- 238000004627 transmission electron microscopy Methods 0.000 description 1
Images
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/30—Particle morphology extending in three dimensions
- C01P2004/32—Spheres
- C01P2004/34—Spheres hollow
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Nanotechnology (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Crystallography & Structural Chemistry (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
- Catalysts (AREA)
Abstract
The application discloses a cerium oxide material and a preparation method and application thereof, belonging to the technical field of nano materials. Dispersing a hard template agent into an organic solvent to obtain a dispersion liquid I, adding a cerium source and a precipitator into water to obtain a mixed liquid II, adding the dispersion liquid I into the mixed liquid II, reacting at a certain temperature, separating, washing, drying and roasting after the reaction is finished to obtain a cerium oxide hollow structure or a cerium oxide core-shell structure; wherein the hard template agent is a polymer or a carbon material. According to the preparation method, the polymer or the carbon material is used as the hard template, and the cerium oxide hollow structure or the cerium oxide core-shell structure with different surface roughness degrees and different structures is prepared by controlling the using amount of the hard template, so that the application of the cerium oxide material in various fields is promoted.
Description
Technical Field
The application relates to the technical field of nano materials, in particular to a cerium oxide material and a preparation method and application thereof.
Background
The rare earth oxide cerium oxide is widely applied at present, and is widely applied to the purification of ultraviolet absorption materials, luminescent materials, glass polishing agents, catalysts, ceramics and automobile exhaust.
With the continuous breakthrough and innovation of people on the research of nano materials in recent years, the nano cerium oxide is found to show special properties, and not only has the properties of the nano materials, but also has the advantages of rare earth oxides. However, the cerium oxide nano-materials with different shapes and structures have different properties, for example, the oxidation capacity of the main active sites {110} and {001} of the cerium oxide nano-rods to carbon monoxide is larger than that of cerium oxide nano-particles with {111} weak active interface.
Therefore, the cerium oxide material with a new shape and structure prepared has great significance for popularization and application.
Disclosure of Invention
According to a first aspect of the present application, there is provided a method of preparing a cerium oxide material, the method comprising:
(1) reacting a mixed solution containing a hard template agent, a cerium source and a precipitator to obtain a precursor;
(2) and roasting the precursor to obtain the cerium oxide material.
Optionally, the hard template agent in step (1) is selected from at least one of a polymer, a carbon material;
the size of the hard template agent is 5 nm-10 mu m;
the hard template agent is in any shape. Hard template agent size in this application refers to the diameter of a spherical hard template agent or the equivalent diameter of an aspherical hard template agent.
Optionally, the polymer is selected from at least one of polystyrene, polyethylene, polypropylene, phenolic resin, and epoxy resin.
Optionally, the hard template agent is added in the step (1) in an amount satisfying:
the mass ratio of the cerium source to the hard template agent is 1-16: 1;
wherein the mass of the cerium source is calculated by the mass of cerium oxide, and the mass of the hard template agent is calculated by the mass of the hard template agent. The upper limit of the mass ratio of the cerium source and the hard template agent is selected from 16, 10, 7.9, 5, 2.5 or 1.7, and the lower limit is selected from 10, 7.9, 5, 2.5, 1.7 or 1.
Optionally, the precipitating agent in step (1) is an amine precipitating agent;
the amine precipitator is at least one selected from hexamethylenetetramine, ethylenediamine and ethanolamine.
Optionally, the cerium source in step (1) is selected from at least one of cerium salts;
the cerium salt comprises at least one of cerium nitrate, cerium chloride, cerium sulfate, cerium acetate and cerium bromide.
Optionally, the mass ratio of the cerium source to the precipitant in the step (1) is 0.1-10: 1. Wherein the upper limit of the mass ratio of the cerium source to the precipitant is selected from 1, 1.7, 2, 4, 6, 8 or 10, and the lower limit is selected from 0.1, 1, 1.7, 2, 4, 6 or 8.
Optionally, the method for obtaining the mixed solution in step (1) includes:
and dropwise adding the dispersion liquid containing the hard template agent into the solution containing the cerium source and the precipitator under the stirring condition to obtain the mixed liquid.
Optionally, the conditions of the reaction in step (1) include:
reacting under stirring;
the reaction temperature is 30-150 ℃;
the reaction time is 5 min-24 h.
Optionally, the conditions of the reaction in step (1) include:
firstly reacting for 5 min-2 h at 0-70 ℃ under the condition of stirring, and then reacting for 5 min-24 h under the condition of condensing reflux. Wherein the upper limit of the stirring reaction temperature can be 70 ℃, 60 ℃, 50 ℃, 40 ℃, 30 ℃, 20 ℃ or 10 ℃, and the lower limit can be 60 ℃, 50 ℃, 40 ℃, 30 ℃, 20 ℃, 10 ℃ or 0 ℃; the condensing reflux temperature is preferably 30-150 ℃, and can be determined according to the selected solvent; the upper limit of the condensation reflux reaction temperature can be selected from 150 ℃, 120 ℃, 100 ℃, 95 ℃, 85 ℃, 75 ℃ or 65 ℃, and the lower limit can be selected from 120 ℃, 100 ℃, 95 ℃, 85 ℃, 75 ℃, 65 ℃, 45 ℃ or 35 ℃.
The crystallinity of cerium oxide is improved by carrying out the reaction at a low temperature and then carrying out the condensation reflux.
Optionally, the concentration of the cerium source in the solution is 4-20 mg/ml.
Optionally, the dispersing agent in the dispersion liquid is selected from at least one of ethanol, acetone, tetrahydrofuran, methanol, isopropanol and dichloromethane;
the solvent in the solution comprises water.
Optionally, the dispersion is obtained in a manner comprising: dispersing the hard template agent into the dispersing agent, and ultrasonically dispersing for 2 min-5 h.
Alternatively, the conditions for the calcination in step (2) include: the roasting temperature is 200-1000 ℃, and the roasting time is 0.5-24 h.
Optionally, the heating rate of the roasting is 0.5-30 ℃/min;
the roasting atmosphere is at least one of air, oxygen, nitrogen, argon and helium.
Optionally, in the step (2), roasting for 0.5-24 hours at 200-1000 ℃ in an oxygen-containing atmosphere to obtain a cerium oxide hollow structure; or
And roasting for 0.5-24 h at 200-1000 ℃ in an oxygen-free atmosphere to obtain the core-shell structure taking carbon as the core and cerium oxide as the shell.
Wherein, the oxygen-free atmosphere is an inert gas atmosphere, which can be selected from but not limited to nitrogen, argon or helium atmosphere. The upper limit of the roasting temperature is selected from 300 ℃, 450 ℃, 550 ℃, 650 ℃, 750 ℃, 850 ℃, 900 ℃ or 1000 ℃; the lower limit is selected from 200 deg.C, 300 deg.C, 450 deg.C, 550 deg.C, 650 deg.C, 750 deg.C, 850 deg.C or 900 deg.C.
In one embodiment:
a preparation method of a cerium oxide hollow structure or a cerium oxide core-shell structure comprises the following steps:
1) dispersing a hard template agent into an organic solvent to obtain a dispersion liquid I, and adding a cerium source and a precipitator into water to obtain a mixed liquid II;
2) adding the dispersion liquid I into the mixed liquid II, and reacting at a certain temperature;
3) after the reaction is finished, separating, washing, drying and roasting to obtain a cerium oxide hollow structure or a cerium oxide core-shell structure;
wherein the hard template agent is a polymer or a carbon material, and the polymer can be a regular polymer or an irregular polymer.
According to the preparation method, the polymer or the carbon material is used as the hard template, and the cerium oxide hollow structure or the cerium oxide core-shell structure with different surface roughness degrees and different structures is prepared by controlling the using amount of the hard template, so that the application of the cerium oxide material in various fields is promoted.
According to a second aspect of the present application, there is provided a cerium oxide material obtained by any one of the above-mentioned preparation methods.
Optionally, the size of the cerium oxide material is 10nm to 5μm。
The cerium oxide material is hollow cerium oxide or a core-shell structure;
the core of the core-shell structure is carbon, and the shell is cerium oxide.
Optionally, the cerium oxide material has a particle size surface roughness Ra of 0.2 to 50.
According to a third aspect of the present application, there is provided a cerium oxide material prepared by any one of the above-mentioned preparation methods or a use of any one of the above-mentioned cerium oxide materials in ultraviolet absorbing materials, luminescent materials, glass polishing agents, catalysts, ceramics, and automobile exhaust purification.
The beneficial effects that this application can produce include:
(1) this application is through adopting polymer or carbon material as hard template, through adjusting the proportion of core hard template and metal Ce, makes the hard template surface cover the metal oxide of different volume, bakes in different atmospheres after that, and the shrink takes place for core hard template, and surface oxide also can have certain shrink along with the core, through the volume of controlling hard template material and surface oxide, can obtain the cerium oxide hollow structure or the cerium oxide nuclear shell structure of not equidimension, different surface roughness.
(2) The cerium oxide ball prepared by the method has a good application prospect in the fields of ultraviolet absorption materials, luminescent materials, glass polishing agents, catalysts, ceramics, automobile exhaust purification and the like, for example, due to the fact that the size and the surface roughness of the core hard template are different, when the cerium oxide ball is applied to a catalyst, a good carrier can be provided for loading of a noble metal catalyst, and exposure of active sites of the catalyst is facilitated.
Drawings
FIG. 1A is a scanning electron micrograph of a cerium oxide hollow structure prepared under the conditions of example 1 of the present invention;
FIG. 1B is a scanning electron micrograph of a cerium oxide hollow structure prepared under the conditions of example 2 of the present invention;
FIG. 1C is a scanning electron micrograph of a cerium oxide hollow structure prepared under the conditions of example 3 according to the present invention;
FIG. 2A is a transmission electron microscope image of a core-shell structure of cerium oxide prepared under the conditions of example 1 of the present invention;
FIG. 2B is a transmission electron microscope image of a core-shell structure of cerium oxide prepared under the conditions of example 2 of the present invention;
fig. 2C is a transmission electron microscope image of a core-shell structure of cerium oxide prepared under the conditions of example 3 of the present invention.
Detailed Description
The present application will be described in detail with reference to examples, but the present application is not limited to these examples.
The raw materials in the examples of the present application were all purchased commercially, unless otherwise specified.
The phenolic resin beads used in examples 1, 3 and 9 and the polystyrene beads used in examples 2 and 10 were obtained from Shanghai Aladdin Biotech Co., Ltd;
the square carbons used in examples 5, 6, 7 were purchased from south-opening catalyst works;
the analysis method in the examples of the present application is as follows:
microscopic morphology analysis was performed using transmission electron microscopy (model HT7700, purchased from HITACHI) and scanning electron microscopy (model Quanta 200F, purchased from FEI);
example 1
(1) 0.2g of the hard template A is dispersed in 30ml of absolute ethyl alcohol by ultrasonic treatment for 2 hours to obtain dispersion liquid. Wherein the hard template A is phenolic resin ball with the size of 1 μm;
(2) adding 0.5g of cerium nitrate and 0.5g of hexamethylenetetramine into 30mL of deionized water to obtain a mixed solution;
(3) gradually dropwise adding the solution obtained in the step (1) into the mixed solution obtained in the step (2) under continuous stirring, and stirring for 2 hours at the temperature of 30 ℃;
(4) condensing and refluxing the mixed solution obtained by stirring in the step (3) at 75 ℃ for 4h, and performing centrifugal separation, washing and drying to obtain a sample;
(5) and (3) roasting the sample obtained in the step (4) by adopting an air roasting method, namely roasting in an air atmosphere, wherein the heating rate is 5 ℃/min, the roasting temperature is 450 ℃, and the time is 5h, and the SEM photo of the prepared cerium oxide is shown in figure 1, and the ATEM photo is shown in figure 2A.
It can be seen from fig. 1A and 2A that the prepared cerium oxide has a hollow spherical structure with a smooth surface.
Example 2
(1) Ultrasonically dispersing 0.1g of the hard template A into 40ml of absolute ethyl alcohol, and ultrasonically treating for 0.5h to obtain a dispersion liquid; wherein the hard template A is a polystyrene sphere with the size of 800 nm;
(2) adding 0.5g of cerium nitrate and 0.5g of hexamethylenetetramine into 50mL of deionized water to obtain a mixed solution;
(3) gradually dropwise adding the solution obtained in the step (1) into the mixed solution obtained in the step (2) under continuous stirring, and stirring for 2 hours at 40 ℃;
(4) condensing and refluxing the mixed solution obtained by stirring in the step (3) at 65 ℃ for 6h, and performing centrifugal separation, washing and drying to obtain a sample;
(5) and (3) roasting the sample obtained in the step (4) by adopting an air roasting method, namely roasting in an air atmosphere, wherein the heating rate is 10 ℃/min, the roasting temperature is 450 ℃, the time is 7h, and the SEM photo of the prepared cerium oxide is shown in the figure 1BTEM photo and is shown in the figure 2B. As can be seen in fig. 1B and 2B, the prepared cerium oxide has an irregular spherical structure with a rough surface;
example 3
(1) Ultrasonically dispersing 0.3g of the hard template A into 50ml of absolute ethyl alcohol, and ultrasonically treating for 1h to obtain a dispersion liquid; wherein the hard template A is a phenolic resin ball with the size of 500 nm;
(2) adding 0.5g of cerium nitrate and 0.5g of hexamethylenetetramine into 60mL of deionized water to obtain a mixed solution;
(3) gradually dropwise adding the solution obtained in the step (1) into the mixed solution obtained in the step (2) under continuous stirring, and stirring for 2 hours at the temperature of 0 ℃;
(4) condensing and refluxing the mixed solution obtained by stirring in the step (3) at 75 ℃ for 4h, and performing centrifugal separation, washing and drying to obtain a sample;
(5) and (3) roasting the sample obtained in the step (4) by adopting an air roasting method, namely roasting in an air atmosphere, wherein the heating rate is 5 ℃/min, the roasting temperature is 450 ℃, the time is 10h, and the SEM photo of the prepared cerium oxide is shown in figure 1 and the CTEM photo is shown in figure 2C. It can be seen in fig. 1C and 2C that the prepared cerium oxide is a surface-roughened porous hollow sphere-shaped cerium oxide with a small particle size.
Example 4
(1) Ultrasonically dispersing 1.0g of the hard template A into 70ml of absolute ethyl alcohol, and ultrasonically treating for 5 hours to obtain a dispersion liquid; wherein the hard template A is a random glycerol epoxy resin template with the size of 5 nm;
(2) adding 0.5g of cerium nitrate and 0.5g of hexamethylenetetramine into 120mL of deionized water to obtain a mixed solution;
(3) gradually dropwise adding the solution obtained in the step (1) into the mixed solution obtained in the step (2) under continuous stirring, and stirring for 5min at 70 ℃;
(4) condensing and refluxing the mixed solution obtained by stirring in the step (3) at 150 ℃ for 5min, and performing centrifugal separation, washing and drying to obtain a sample;
(5) and (4) roasting the sample obtained in the step (4) by adopting an air roasting method, namely roasting in an air atmosphere, wherein the heating rate is 0.5 ℃/min, the roasting temperature is 1000 ℃, and the time is 0.5h, and the prepared cerium oxide is of a hollow spherical structure with a smooth surface.
Example 5
(1) Ultrasonically dispersing 0.063g of the hard template A into 10ml of absolute ethyl alcohol, and ultrasonically treating for 2min to obtain a dispersion liquid; wherein the hard template A is square carbon with the size of 10 μm;
(2) adding 0.5g of cerium nitrate and 0.5g of hexamethylenetetramine into 30mL of deionized water to obtain a mixed solution;
(3) gradually dropwise adding the solution obtained in the step (1) into the mixed solution obtained in the step (2) under continuous stirring, and stirring for 2 hours at the temperature of 0 ℃;
(4) condensing and refluxing the mixed solution obtained by stirring in the step (3) at 70 ℃ for 24h, and performing centrifugal separation, washing and drying to obtain a sample;
(5) and (4) roasting the sample obtained in the step (4) by adopting an air roasting method, namely roasting in air atmosphere, wherein the heating rate is 30 ℃/min, the roasting temperature is 200 ℃, and the time is 24 hours, so that the cerium oxide with a hollow spherical structure with a smooth surface is prepared.
Example 6
(1) Ultrasonically dispersing 0.1g of the hard template A into 30ml of absolute ethyl alcohol, and ultrasonically treating for 30min to obtain a dispersion liquid; wherein the hard template A is polygonal carbon with the size of 1 micron;
(2) adding 0.1g of cerium nitrate and 0.01g of hexamethylenetetramine into 5mL of deionized water to obtain a mixed solution;
(3) gradually dropwise adding the solution obtained in the step (1) into the mixed solution obtained in the step (2) under continuous stirring, and stirring for 2 hours at 60 ℃;
(4) condensing and refluxing the mixed solution obtained by stirring in the step (3) at 120 ℃ for 30min, and performing centrifugal separation, washing and drying to obtain a sample;
(5) and (4) roasting the sample obtained in the step (4) by adopting an air roasting method, namely roasting in air atmosphere, wherein the heating rate is 20 ℃/min, the roasting temperature is 300 ℃, and the time is 20h, and the prepared cerium oxide is of a hollow spherical structure with a smooth surface.
Example 7
(1) Ultrasonically dispersing 0.01g of a hard template A into 10ml of absolute ethyl alcohol, and ultrasonically treating for 10min to obtain a dispersion liquid; wherein the hard template A is a carbon sphere with the size of 1 μm;
(2) adding 0.1g of cerium nitrate and 0.06g of hexamethylenetetramine into 10mL of deionized water to obtain a mixed solution;
(3) gradually dropwise adding the solution obtained in the step (1) into the mixed solution obtained in the step (2) under continuous stirring, and stirring for 2 hours at the temperature of 30 ℃;
(4) condensing and refluxing the mixed solution obtained by stirring in the step (3) at 75 ℃ for 7h, and performing centrifugal separation, washing and drying to obtain a sample;
(5) and (4) roasting the sample obtained in the step (4) by adopting an air roasting method, namely roasting in an air atmosphere, wherein the heating rate is 20 ℃/min, the roasting temperature is 750 ℃, and the time is 2 hours, and the prepared cerium oxide is of a hollow spherical structure with a smooth surface.
Example 8
(1) Ultrasonically dispersing 0.2g of the hard template A into 40ml of absolute ethyl alcohol, and ultrasonically treating for 2 hours to obtain a dispersion liquid; wherein the hard template A is irregular cyanuric acid epoxy resin with the size of 2 μm;
(2) adding 1g of cerium nitrate and 0.1g of hexamethylenetetramine into 100mL of deionized water to obtain a mixed solution;
(3) gradually dropwise adding the solution obtained in the step (1) into the mixed solution obtained in the step (2) under continuous stirring, and stirring for 2 hours at 50 ℃;
(4) condensing and refluxing the mixed solution obtained by stirring in the step (3) at 95 ℃ for 4h, and performing centrifugal separation, washing and drying to obtain a sample;
(5) and (4) roasting the sample obtained in the step (4) by adopting an air roasting method, namely roasting in air atmosphere, wherein the heating rate is 10 ℃/min, the roasting temperature is 850 ℃, and the time is 10 hours, and the prepared cerium oxide is of a hollow spherical structure with a smooth surface.
Example 9
(1) Ultrasonically dispersing 0.2g of the hard template A into 30ml of absolute ethyl alcohol, and ultrasonically treating for 3 hours to obtain a dispersion liquid; wherein the hard template A is phenolic resin ball with the size of 5 μm;
(2) adding 0.5g of cerium nitrate and 0.5g of hexamethylenetetramine into 30mL of deionized water to obtain a mixed solution;
(3) gradually dropwise adding the solution obtained in the step (1) into the mixed solution obtained in the step (2) under continuous stirring, and stirring for 2 hours at 60 ℃;
(4) condensing and refluxing the mixed solution obtained by stirring in the step (3) at 70 ℃ for 8h, and performing centrifugal separation, washing and drying to obtain a sample;
(5) and (4) roasting the sample obtained in the step (4) by adopting an air roasting method, namely roasting in air atmosphere, wherein the heating rate is 15 ℃/min, the roasting temperature is 550 ℃, and the time is 5h, and the prepared cerium oxide is of a hollow spherical structure with a smooth surface.
Example 10
(1) Ultrasonically dispersing 0.2g of the hard template A into 40ml of absolute ethyl alcohol, and ultrasonically treating for 4 hours to obtain a dispersion liquid; wherein the hard template A is a polystyrene sphere with the size of 200 nm;
(2) adding 0.1g of cerium nitrate and 0.1g of hexamethylenetetramine into 30mL of deionized water to obtain a mixed solution;
(3) gradually dropwise adding the solution obtained in the step (1) into the mixed solution obtained in the step (2) under continuous stirring, and stirring for 2 hours at 60 ℃;
(4) condensing and refluxing the mixed solution obtained by stirring in the step (3) at 85 ℃ for 10h, and performing centrifugal separation, washing and drying to obtain a sample;
(5) and (4) roasting the sample obtained in the step (4) by adopting an air roasting method, namely roasting in air atmosphere, wherein the heating rate is 7 ℃/min, the roasting temperature is 650 ℃, and the time is 5h, and the prepared cerium oxide is of a hollow spherical structure with a smooth surface.
Example 11
The preparation method of this example is the same as that of example 1, except that the calcination is performed in a nitrogen atmosphere to obtain a cerium oxide core-shell structure, wherein cerium oxide is a shell and carbon is a core.
Example 12
The preparation method of this example is the same as that of example 2, and the only difference is that the calcination is performed in a nitrogen atmosphere to obtain a cerium oxide core-shell structure, wherein cerium oxide is used as a shell and carbon is used as a core.
Example 13
The preparation method of this example is the same as that of example 5, except that the calcination is performed in a nitrogen atmosphere to obtain a cerium oxide core-shell structure, wherein cerium oxide is a shell and carbon is a core.
Example 14
The preparation method of the embodiment is the same as that of embodiment 1, and the only difference is that the step (3) is directly subjected to centrifugal separation, washing and drying after being stirred for 2 hours at 30 ℃ to obtain a sample; the structure of the finally obtained cerium oxide is similar to that of the cerium oxide in FIG. 1A, and the cerium oxide is a hollow spherical structure with a smooth surface, but the crystallinity is different.
Example 15 topography characterization
As can be seen from fig. 1 to 2, the cerium oxide materials provided in embodiments 1 to 10 of the present application have a hollow structure, and embodiments 11 to 14 form a core-shell structure, the diameter of which is 500nm to 3 μm, wherein cerium oxide is a shell and carbon is a core in the core-shell structure.
And (3) performance testing:
the cerium oxide structures provided in the examples were subjected to performance testing by using AFM (Atomic Force Microscope), and the surface roughness of the cerium oxide obtained in each example was Ra 0.2 to 50.
Therefore, the cerium oxide hollow structure or the core-shell structure prepared by the method is suitable for application in the fields of ultraviolet absorption materials, luminescent materials, glass polishing agents, catalysts, ceramics, automobile exhaust purification and the like.
Although the present application has been described with reference to a few embodiments, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the application as defined by the appended claims.
Claims (10)
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